FI116675B - Cyclopentadienylmagnesium bridges, process for their preparation and their use in the preparation of metallocenes - Google Patents
Cyclopentadienylmagnesium bridges, process for their preparation and their use in the preparation of metallocenes Download PDFInfo
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- FI116675B FI116675B FI950871A FI950871A FI116675B FI 116675 B FI116675 B FI 116675B FI 950871 A FI950871 A FI 950871A FI 950871 A FI950871 A FI 950871A FI 116675 B FI116675 B FI 116675B
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- bis
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000011777 magnesium Substances 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 10
- -1 penta dienyl compounds Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 125000005013 aryl ether group Chemical group 0.000 claims description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 150000002681 magnesium compounds Chemical class 0.000 claims 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 239000003208 petroleum Substances 0.000 claims 1
- MHYQBXJRURFKIN-UHFFFAOYSA-N C1(C=CC=C1)[Mg] Chemical class C1(C=CC=C1)[Mg] MHYQBXJRURFKIN-UHFFFAOYSA-N 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- WFZFDWAAGYEXOS-UHFFFAOYSA-N 1,2,3-trimethylcyclopenta-1,3-diene Chemical compound CC1=C(C)C(C)=CC1 WFZFDWAAGYEXOS-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IRAWLGHJHQBREM-UHFFFAOYSA-N 7-Methylinden Natural products CC1=CC=CC2=C1C=CC2 IRAWLGHJHQBREM-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910007928 ZrCl2 Inorganic materials 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000015895 biscuits Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- SEYQGVYTVHINPB-UHFFFAOYSA-N 2,3-dimethoxyfuran Chemical compound COC=1C=COC=1OC SEYQGVYTVHINPB-UHFFFAOYSA-N 0.000 description 1
- LKZLPIZLLSVDSM-UHFFFAOYSA-N C1=CC2=CC=CC=C2C1[Mg]C1C2=CC=CC=C2C=C1[SiH](C)C Chemical compound C1=CC2=CC=CC=C2C1[Mg]C1C2=CC=CC=C2C=C1[SiH](C)C LKZLPIZLLSVDSM-UHFFFAOYSA-N 0.000 description 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- ZKSADANYBSWZAB-UHFFFAOYSA-N CCCCCC[Mg]CCCCCC Chemical compound CCCCCC[Mg]CCCCCC ZKSADANYBSWZAB-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- RINBNPVERYAXQO-UHFFFAOYSA-N bis(1H-inden-1-yl)silane Chemical compound C1=CC2=CC=CC=C2C1[SiH2]C1C2=CC=CC=C2C=C1 RINBNPVERYAXQO-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- VCTCXZDCRFISFF-UHFFFAOYSA-N magnesium;butane;butane Chemical compound [Mg+2].CCC[CH2-].CC[CH-]C VCTCXZDCRFISFF-UHFFFAOYSA-N 0.000 description 1
- YHNWUQFTJNJVNU-UHFFFAOYSA-N magnesium;butane;ethane Chemical compound [Mg+2].[CH2-]C.CCC[CH2-] YHNWUQFTJNJVNU-UHFFFAOYSA-N 0.000 description 1
- KXDANLFHGCWFRQ-UHFFFAOYSA-N magnesium;butane;octane Chemical compound [Mg+2].CCC[CH2-].CCCCCCC[CH2-] KXDANLFHGCWFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
Syklopentadienyylimagnesiumsiltayhdisteitä, menetelmiä niiden valmistamiseksi ja niiden käyttö metalloseenien valmistukseen 116675 5 Tämä keksintö koskee uusia syklopentadienyyli- magnesiumsiltayhdisteitä, joilla on yleinen kaava Q(CpRa) (Cp'R'a>)Mg, menetelmiä niiden valmistamiseksi sekä niiden käyttöä sillan käsittävien metalloseenien valmistukseen .This invention relates to novel cyclopentadienyl magnesium bridge compounds of the general formula Q (CpRa) (Cp'R'a>) Mg, processes for their preparation and their use in the preparation of metallocenes comprising bridges.
10 Yleisen kaavan Q(CpRa) (Cp'R'a.)Mg mukaisia yhdis teitä valmistetaan saattamalla syklopentadienyylisiltayh-disteet reagoimaan yhtälön Q(CpRa) (Cp’R'a.) + (R3R4) cMg ->Compounds of general formula Q (CpRa) (Cp'R'a.) Mg are prepared by reacting cyclopentadienyl bridge compounds with Q (CpRa) (Cp'R'a.) + (R 3 R 4) cMg ->
15 Q (CpRa) (Cp ' R' a>) Mg + CR3H + CR4H15 Q (CpR a) (C p 'R' a>) Mg + CR 3 H + CR 4 H
mukaan.by.
Yleisen kaavan Q(CpRa) (Cp'R'a.)Mg mukaiset yhdisteet ovat sellaisia yhdisteitä, joilla on yleinen kaava 20 (1) Q(CpRa) (Cp ' R ' a') Mg (1) ;·ι jossa • · · *Vt Cp = sykiopentadienyyli- tai indenyyliryhmä, » · · 25 R, R' = alkyyli-, fosfiini-, amiini-, alkyylieet- teri- tai aryylieetteriryhmiä ja 0 < a < 4, 0 < a' <4, • * · 'C : Cp' = jokin ryhmistä Cp tai *·' * Cp' = NR", jossa R" = alkyyli- tai aryyliryhmä, ja a' = 0 ja Q on yksi- tai useampiarvoinen silta * * jj : 30 Cp:n ja Cp':n välillä, jolloin • · · 1 1 2 Q = (R1—Z-R2)bCompounds of general formula Q (CpRa) (Cp'R'a.) Mg are compounds of general formula 20 (1) Q (CpRa) (Cp 'R' a ') Mg (1); · · * Vt Cp = cyclopentadienyl or indenyl group, · · 25 R, R ′ = alkyl, phosphine, amine, alkyl ether or aryl ether groups and 0 <a <4, 0 <a '<4, • * · 'C: Cp' = one of the groups Cp or * · '* Cp' = NR "where R" = an alkyl or aryl group and a '= 0 and Q is a monovalent bridge * * jj: 30 Cp and Cp ', where • · · 1 1 2 Q = (R1-Z-R2) b
*.·,· I*. ·, · I
35 • * · : .·. jolloin R1 ja R2 ovat samoja tai erilaisia ja tarkoittavat ,···, vetyatomia, Ci-10-alkyyliryhmää, C6-i0-aryyliryhmää ja Z hii- *** liatomia, piitä tai germaniumia, jolloin b = 1, 2 tai 3.35 • * ·:. ·. wherein R 1 and R 2 are the same or different and represent, ···, a hydrogen atom, a C 1 -C 10 alkyl group, a C 6 -C 10 aryl group, and Z a carbon atom, silicon or germanium, where b = 1, 2 or 3.
116675 2 Nämä yhdisteet kuuluvat tunnettuun tekniikan tasoon ja niitä on kuvattu julkaisuissa EP-A 0 480 390, EP-A 0 413 326, EP-A 0 530 908, EP-A 0 344 887, EP-A 0 420 436, EP-A 0 416 815, EP-A 0 520 732.These compounds belong to the prior art and are described in EP-A 0 480 390, EP-A 0 413 326, EP-A 0 530 908, EP-A 0 344 887, EP-A 0 420 436, A 0 416 815, EP-A 0 520 732.
5 Niitä voidaan valmistaa näissä julkaisuissa sekä julkaisussa DE-A 44 02 192 kuvattujen menetelmien mukaan.They may be prepared according to the methods described in these publications and in DE-A 44 02 192.
Esimerkkejä keksinnön mukaisesti käytettävistä bissyklopentadienyylisiltayhdisteistä ovat dimetyylisilyy-li-bis-(1-indeeni), dimetyylisilyyli-bis-(1-syklopentadi-10 eeni), 2,2-propyyli-bis-(1-indeeni), 2,2-propyyli-bis (tri- metyylisyklopentadieeni), 2,2-propyyli-bis-(5-dimetyyli- amino-1-indeeni), 2,2-propyyli-bis-(6-dipropyyliamino-l- indeeni), 2,2-propyyli-bis-(4,7-bis(dimetyyliamino-1-indeeni) , 2,2-propyyli-bis-(5-difenyylifosfiino-l-indeeni), 15 2,2-propyyli-bis-(4,5,6,7-tetrahydro-l-indeeni), 2,2-propyyli-bis- (4-metyyli-l-indeeni) , 2,2-propyyli-bis-(5-metyyli-1-indeeni ) , 2,2-propyyli-bis-(6-metyyli-1-indeeni), 2,2-propyyli-bis-(7-metyyli-l-indeeni) , 2,2-propyyli-bis- (5-metoksi-1-indeeni) , 2,2-propyyli-bis-(4,7-dimetoksi-l-20 indeeni), 2,2-propyyli-bis-(2,3-dimetyyli-l-indeeni), 2,2-propyyli-bis-(4,7-dimetyyli-l-indeeni) , 2,2-propyyli-bis- (9-fluoreeni) , 2,2-propyyli-bis-(1-syklopentadieeni) , ;·, 2,2-propyyli-bis-(1-indeeni) , 2,2-propyyli-bis-(1-indeeni) - * ♦ · f.. (1-syklopentadieeni), difenyylimetyyli-bis-(1-indeeni), * * * *.* 25 difenyylimetyyli-bis-(1-syklopentadieeni) , difenyylimetyy- • · /·;* li-bis-(1-indeeni) , difenyylimetyyli-bis-(1-indeeni)(1- · syklopentadieeni) , difenyylisilyyli-bis-(1-indeeni) , dife-* · · * nyylisilyyli-bis-(1-syklopentadieeni) , difenyylisilyyli-bis-(1-indeeni), difenyylisilyyli-bis-(1-indeeni)(1-syklo- tj j 30 pentadieeni) , etyleeni-bis-(1-indeeni) , etyleeni-bis-(tri- metyylisyklopentadieeni) , etyleeni-bis- (5-dimetyyliamino-1-indeeni), etyleeni-bis-(6-dipropyyliamino-l-indeeni) , * * * etyleeni-bis-(4,7-bis-(dimetyyliamino) -1-indeeni) , etylee-'y' ni-bis-(5-difenyylifosfiino-l-indeeni) , etyleenibis-(4,5,- *. : : 35 6, 7-tetrahydro-l-indeeni) , etyleeni-bis-(4-metyyli-l-in- deeni), etyleeni-bis-(5-metyyli-l-indeeni), etyleeni-bis- 116675 3 (6-metyyli-l-indeeni), etyleeni-bis-(7-metyyli-l-indeeni) , etyleeni-bis-(5-metoksi-l-indeeni), etyleenibis-(4,7-dime-toksi-l-indeeni), etyleeni-bis-(2,3-dimetyyli-l-indeeni) , etyleeni-bis-(4,7-dimetyyli-l-indeeni) , etyleeni-bis-(9-5 fluoreeni), etyleeni-bis-(1-syklopentadieeni) , etyleeni-bis- (1-indeeni), etyleeni-bis-(1-indeeni)-(1-syklopentadieeni) , dimetyylisilyyli-bis-(1-indeeni) , dimetyylisilyy-li-bis-(1-indeeni)(1-syklopentadieeni).Examples of the bicyclopentadienyl bridge compounds used in the invention are dimethylsilyl-bis- (1-indene), dimethylsilyl-bis- (1-cyclopentadine-10-ene), 2,2-propyl-bis- (1-indene), 2,2-propyl -bis (trimethylcyclopentadiene), 2,2-propyl-bis- (5-dimethylamino-1-indene), 2,2-propyl-bis- (6-dipropylamino-1-indene), 2,2- propyl bis- (4,7-bis (dimethylamino-1-indene), 2,2-propyl bis- (5-diphenylphosphino-1-indene), 2,2-propyl bis- (4,5, 6,7-tetrahydro-1-indene), 2,2-propyl-bis- (4-methyl-1-indene), 2,2-propyl-bis- (5-methyl-1-indene), 2,2 -propyl-bis- (6-methyl-1-indene), 2,2-propyl-bis- (7-methyl-1-indene), 2,2-propyl-bis- (5-methoxy-1-indene) , 2,2-propyl-bis- (4,7-dimethoxy-1-indene), 2,2-propyl-bis- (2,3-dimethyl-1-indene), 2,2-propyl-bis- (4,7-Dimethyl-1-indene), 2,2-propyl-bis- (9-fluorene), 2,2-propyl-bis- (1-cyclopentadiene), ·, 2,2-propyl-bis - (1-indene), 2,2-propyl-bis- (1-indene) - · D .. (1-cyclopentadiene), diphenylmethyl-bis- (1-indene), * * * *. * Diphenylmethyl-bis- (1-cyclopentadiene), diphenylmethyl-· · / ·; * 1-bis- ( 1-indene), diphenylmethyl-bis- (1-indene) (1-cyclopentadiene), diphenylsilyl-bis- (1-indene), diphenylsilyl-bis- (1-cyclopentadiene), diphenylsilyl-bis - (1-indene), diphenylsilyl-bis- (1-indene) (1-cyclo and pentadiene), ethylene-bis- (1-indene), ethylene-bis- (trimethylcyclopentadiene), ethylene-bis - (5-dimethylamino-1-indene), ethylene-bis- (6-dipropylamino-1-indene), * * * ethylene-bis- (4,7-bis- (dimethylamino) -1-indene), ethyl- 'y' ni-bis- (5-diphenylphosphino-1-indene), ethylenebis- (4,5, *). :: 35 6,7-Tetrahydro-1-indene), ethylene-bis- (4-methyl-1-indene), ethylene-bis- (5-methyl-1-indene), ethylene-bis-116675 3 (6-methyl-1-indene), ethylene-bis- (7-methyl-1-indene), ethylene-bis- (5-methoxy-1-indene), ethylene-bis- (4,7-dimethoxy-1) -indene), ethylene-bis- (2,3-dimethyl-1-indene), ethylene-bis- (4,7-dimethyl-1-indene), ethylene-bis- (9-5 fluorene), ethylene-bis - (1-cyclopentadiene), ethylene-bis- (1-indene), ethylene-bis- (1-indene) - (1-cyclopentadiene), dimethylsilyl-bis- (1-indene), dimethylsilyl-bis- ( 1-indene) (1-cyclopentadiene).
Yhdisteinä (R3R4)cMg käytetään sellaisia, joissa R3 10 ja R4 ovat samoja tai erilaisia ja tarkoittavat vetyä H, Ci-12-alkyyliryhmiä ja c = 0 tai 1. Keksinnön mukaisesti edullisia ovat butyylietyylimagnesium, di-n-butyylimag-nesium, di-n-heksyylimagnesium, n-butyyli-sek-butyylimag-nesium kaupallisina valmistemuotoinaan, kuten esimerkiksi 15 BOMAGr-A, valmistaja Witco GmbH (butyylioktyylimagnesium, 20-prosenttinen heptaanissa). Tässä tapauksessa reaktion etenemiseen ei tarvita mitään lisäliuotinta. Reaktion kulkua voidaan seurata kaasunkehityksen avulla.The compounds (R3R4) cMg are those wherein R310 and R4 are the same or different and represent hydrogen, H, C1-12 alkyl groups and c = 0 or 1. According to the invention, butylethylmagnesium, di-n-butylmagnesium, di- n-hexylmagnesium, n-butyl sec-butyl magnesium in commercial forms such as BOMAGr-A, manufactured by Witco GmbH (butyl octyl magnesium, 20% in heptane). In this case, no additional solvent is required for the reaction to proceed. The course of the reaction can be monitored by gas evolution.
Edukteja käytetään edullisesti stoikiometrisina 20 määrinä.The eductants are preferably used in stoichiometric amounts.
Reaktiot tapahtuvat inertin kaasun atmosfäärissä ja hapelta ja kosteudelta eristettyinä. Tällöin komponentit laitetaan keksinnön mukaisesti edullisesti huoneenläm- , Potilassa inerttiin liuottimeen ja lämpötilaa kohotetaan * » 25 samalla voimakkaasti sekoittaen.The reactions take place in an atmosphere of inert gas and isolated from oxygen and moisture. In accordance with the invention, the components are preferably placed in a room temperature, potila inert solvent and the temperature is raised to 25 with vigorous stirring.
Inertteinä liuottimina käyttökelpoisia ovat tällä : alalla tavalliset liuottimet kuten esimerkiksi alifaatti- V ’ set ja/tai sykliset eetterit tai alifaattiset ja/tai aro maattiset hiilivedyt.Useful inert solvents include: solvents commonly used in the art such as aliphatic V 'and / or cyclic ethers or aliphatic and / or aromatic hydrocarbons.
: : : 30 Keksinnön mukaisesti edullisia ovat alifaattiset • · * · hiilivedyt, joiden kiehumispisteet ovat > 60 °C, edulli- sesti > 80 °C, erityisesti alueella 80 - 120 °C. Reaktio • * i — i » t toteutetaan käytännöllisten reaktioaiko j en saavuttamiseksi ‘y’ edullisesti liuottimien kiehumispisteessä, erityisesti vä- : 35 Iillä 80 - 120 °C. Liuottimen määrä ei ole erityisen f l I i kriittinen. Suurten tila-aika -saantojen saavuttamiseksi 116675 4 työskennellään kuitenkin ylemmällä teknisesti mahdollisella alueella.According to the invention, aliphatic hydrocarbons having boiling points> 60 ° C, preferably> 80 ° C, in particular in the range 80-120 ° C, are preferred. The reaction is carried out to give practical reaction times 'y' preferably at the boiling point of the solvents, in particular at 80-120 ° C. The amount of solvent is not particularly critical. However, to achieve high space-time yields, 116675 4 is working in the upper technically feasible area.
Keksinnön kohteena ovat sen vuoksi yhdisteet, joilla on yleinen kaava (1) 5 Q(CpRa) (Cp’RV)Mg (1) j ossaThe invention therefore relates to compounds of general formula (1) 5 Q (CpRa) (Cp'RV) in Mg (1)
Cp = syklopentadienyyli- tai indenyyliryhmä, 10 R, R' = alkyyli-, fosfiini-, amiini-, alkyylieet- teri- tai aryylieetteriryhmiä ja 0 < a < 4, 0 < a' < 4,Cp = cyclopentadienyl or indenyl group, 10 R, R '= alkyl, phosphine, amine, alkyl ether or aryl ether groups and 0 <a <4, 0 <a' <4,
Cp' = jokin ryhmistä Cp taiCp '= one of the groups Cp or
Cp' = NR", jossa R" = alkyyli- tai aryyliryhmä,ja a' = 0 ja Q on yksi- tai useampiarvoinen silta 15 Cp:n ja Cp':n välillä, jolloin Q = (R1—Z—R2) b 20 jolloin R1 ja R4 ovat samoja tai erilaisia ja tarkoittavat vetyatomia, Ci_i0-alkyyliryhmää, C6_i0-aryyliryhmää ja Z hiiliatomia, piitä tai germaniumia, jolloin b = 1, 2 tai 3.Cp '= NR ", where R" = alkyl or aryl group, and a' = 0 and Q is a monovalent bridge between Cp and Cp ', where Q = (R1-Z-R2) b Wherein R 1 and R 4 are the same or different and represent a hydrogen atom, a C 1-10 alkyl group, a C 6-10 aryl group and Z a carbon atom, silicon or germanium, where b = 1, 2 or 3.
Keksinnön toisena kohteena on menetelmä yleisen : '* 25 kaavan Q(CpRa) (Cp'R'a-)Mg mukaisten yhdisteiden valmistami- ·.·.· seksi, jolloin merkinnöillä Q, Cp, R, Cp', R' ja a, a' on I ! » patenttivaatimuksessa 1 annettu merkitys, jossa menetel- : mässä yleisen kaavan Q(CpRa) (Cp'R'a>) mukaiset syklopenta- dienyylisiltayhdisteet saatetaan reagoimaan inertin liuot- 30 timen läsnä ollessa kaavan (R3R4)cMg mukaisen magnesiumyh- ; ,*, disteen kanssa, jolloin R3R4 voivat tarkoittaa toisistaan * > * riippumatta vetyä H, Ci-12-alkyyliryhmiä ja c = 0 tai 1.Another object of the invention is a process for the preparation of compounds of the general formula: (*) Q (CpRa) (Cp'R'a-) Mg, wherein Q, Cp, R, Cp ', R' and a , I'm on! The meaning given in claim 1, wherein the process comprises reacting a cyclopentadienyl bridge compound of the general formula Q (CpRa) (Cp'R'a>) in the presence of an inert solvent with a magnesium group of the formula (R3R4) cMg; , *, with a distillate wherein R3R4 may independently represent *> * hydrogen, H, C1-12 alkyl groups, and c = 0 or 1.
1 ·1 ·
Muut kohteet ovat tunnettuja muiden patenttivaati- t · V,'· musten perusteella.Other objects are known from other patent claims.
35 Yleisen kaavan (1) Q(CpRa) (Cp'R'a.)Mg mukaiset kek- ; sinnön yhdisteet ovat arvokkaita lähtöaineita metallosee- nien valmistukselle. Metalloseeneillä tarkoitetaan keksin 116675 5 nön mukaisesti sekä sandwich-komplekseja että puolisand-wich-komplekseja.A biscuit of general formula (1) Q (CpRa) (Cp'R'a.) Mg; The compounds of the invention are valuable starting materials for the production of metallocenes. By metallocenes is meant both sandwich and semi-sandwich complexes according to biscuit 116675.
Näitä metalloseenejä valmistetaan saattamalla yleisen kaavan (1) mukaiset yhdisteet reagoimaan sellais-5 ten yhdisteiden kanssa, joilla on yleinen kaava M(X)m, jossa M on siirtymämetalli alkuaineiden jaksollisen järjestelmän ryhmistä 3-8 (IUPAC-merkintä), erityisesti Ti, Zr, Hf, Fe, ja m on metallin M hapetusluku ja X voi olla halogeeni, erityisesti Cl tai Br.These metallocenes are prepared by reacting compounds of general formula (1) with compounds of general formula M (X) m wherein M is a transition metal from groups 3-8 of the Periodic Table of the Elements, especially Ti, Zr , Hf, Fe, and m are the oxidation number of the metal M and X may be halogen, especially Cl or Br.
10 Reaktio tapahtuu edullisesti sellaisten inerttien eetterien läsnä ollessa kuin alifaattiset, sykloalifaatti-set ja/tai aromaattiset eetterit kuten dietyylieetteri, metyyli-tert-butyylieetteri, tetrahydrofuraani, dimetoksi-furaani, dimetoksietaani, inertit alifaattiset ja/tai aro-15 maattiset hiilivedyt kuten heksaani, heptaani, oktaani, tolueeni, ksyleeni.The reaction is preferably carried out in the presence of inert ethers such as aliphatic, cycloaliphatic and / or aromatic ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dimethoxyfuran, dimethoxyethane, inert aliphatic and / or heptane, octane, toluene, xylene.
Edullisia ovat eetterit ja hiilivedyt, joihin lopputuotteet ovat liukoisia.Ethers and hydrocarbons to which the end products are soluble are preferred.
Reagoivien aineiden sekoitus voi tapahtua julkai-20 suissa EP-A 0 420 436 ja EP-A 0 416 815 kuvattujen menetelmien mukaan.The reactants may be mixed according to the methods described in EP-A 0 420 436 and EP-A 0 416 815.
• Keksinnön mukaisesti menetellään kuitenkin edulli- :·, sesti niin, että siirtymämetallihalogenidi laitetaan eet- • · · teriin tai aromaattiseen hiilivetyyn ja kaavan (1) mukais- !.! 25 ten yhdisteiden valmistukseen tarvittava reaktioseos an- i · // nostellaan suoraan eli ilman edeltävää jatkokäsittelyä tai i « · :··(·' eristystä edullisesti stoikiometrisinä määrinä. Reak- * * » V * tiolämpötila valitaan lähtöaineyhdisteestä riippuen ja se voi olla välillä n. -70 °C - n. 120 °C. Keksinnön mukai- ,· · 30 sesti edullisia ovat lämpötilat -20 - +20 °C.However, according to the invention, it is preferred to: place the transition metal halide in an ether or an aromatic hydrocarbon and according to formula (1). The reaction mixture required for the preparation of the compounds is reacted directly, i.e. without further processing or isolation, preferably in stoichiometric amounts. The reaction temperature is chosen depending on the starting compound and may be between -70 ° C to about 120 ° C According to the invention, temperatures of -20 ° C to + 20 ° C are preferred.
Jatkokäsittely tapahtuu erottamalla magnesiumsuo-lat ja eristämällä metalloseeni tavallisella tavalla tällä * * · !,; alalla tunnetuilla menetelmillä.Further treatment is effected by separating the magnesium salts and isolating the metallocene in the usual way with this * * ·!,; by methods known in the art.
t > 'Esimerkkejä * * | 35 Kaikki kokeet suoritettiin hapelta ja kosteudelta suojattuina inertin kaasun atmosfäärissä.t> 'Examples * * | 35 All experiments were performed under inert gas, protected from oxygen and moisture.
6 1 1 66756 1 1 6675
Esimerkki 1Example 1
Etyleeni-bis-(indenyyli)magnesiumin valmistus: 10 g indeeniä (95-prosenttinen; 82 mmol) sekoitettiin 34,2 g:n kanssa B0MAGR-A:ta (20-prosenttinen hep-5 taanissa; 41 mmol) 100 ml:n lasikolvissa huoneenlämpötilassa ja sen jälkeen sitä kuumennettiin refluksoiden 4 tunnin ajan.Preparation of ethylene-bis- (indenyl) magnesium: 10 g indene (95%; 82 mmol) was mixed with 34.2 g B0MAGR-A (20% hept-5; 41 mmol) in 100 mL in a glass flask at room temperature and then heated at reflux for 4 hours.
Sitten huoneenlämpötilassa lisättiin 7,7 g (41 mmol) 1,2-dibromietaania ja 5,3 g (41 mmol) di-n-butyyli-10 eetteriä ja sekoitettiin vielä 3 tuntia refluksoiden.Then, at room temperature, 7.7 g (41 mmol) of 1,2-dibromoethane and 5.3 g (41 mmol) of di-n-butyl-10 ether were added and stirred for a further 3 hours under reflux.
Niin valmistettu etyleeni-bis-(indenyylin) liuos erotettiin sen jälkeen suodattamalla saostuneesta MgBr2:sta.The ethylene-bis (indenyl) solution so prepared was then separated by filtration from the precipitated MgBr 2.
Suodos sekoitettiin 34,2 g:n kanssa BOMAGR-A:ta (20-prosenttinen heptaanissa; 41 mmol) ja refluksoitiin 4 tuntia. 15 Jäähdytettiin lämpötilaan -10 °C ja suodatettiin.The filtrate was mixed with 34.2 g BOMAGR-A (20% in heptane; 41 mmol) and refluxed for 4 hours. Cooled to -10 ° C and filtered.
Suodatusjäännös kuivattiin alennetussa paineessa (100 °C/0,1 mbar).The filtrate residue was dried under reduced pressure (100 ° C / 0.1 mbar).
Voitiin eristää 11,3 g (98 % teoreettisesta) väritöntä kiintoainetta.11.3 g (98% of theory) of a colorless solid could be isolated.
20 Etyleeni-bis-(indenyyli)magnesium:20 Ethylene-bis- (indenyl) magnesium:
Mg: (laskettu: 8,66 %) saatu: 8,56 % , 1H—NMR: (DMSO) 7,2 (m, 2H) ; 7,0 (m, 2H) ; 6,4 (d, 2H) ; 6,2 (m, 4H) ; 5,6 (d, 2H) ; 3,0 (s, 4H) .Mg: (calculated: 8.66%) found: 8.56%, 1 H NMR: (DMSO) 7.2 (m, 2H); 7.0 (m, 2H); 6.4 (d, 2H); 6.2 (m. 4H); 5.6 (d, 2H); 3.0 (s, 4H).
Esimerkki 2 I f ♦ 1 · ’·'·1 25 Dimetyylisilyyli-bis- (indenyyli)magnesiumin val- mistus : 12,2 g indeeniä (95-prosenttinen; 0,1 mmol) sekoi- !,·1 · tettiin 42 g: n kanssa BOMAGR-A:ta (2 0-prosenttinen hep taanissa; 50 mmol) huoneenlämpötilassa ja sen jälkeen sitä > 30 r e f luks o i t i in 4 tunnin ajan. Sitten huoneenlämpötilassa i < 1 · lisättiin 6,45 g Me2SiCl2:ta (50 mmol) ja 6,5 g (50 mmol) • · ♦ di-n-butyylieetteriä ja refluksoitiin vielä 2 tuntia.Example 2 Preparation of dimethylsilyl-bis- (indenyl) magnesium: 12.2 g of indene (95%; 0.1 mmol) was mixed with 42 g of indene. with BOMAGR-A (20% in heptane; 50 mmol) at room temperature and then refluxed for> 4 hours. Then at room temperature i <1 · 6.45 g of Me2SiCl2 (50 mmol) and 6.5 g (50 mmol) of di-n-butyl ether were added and refluxed for a further 2 hours.
» 1 · '1·’ Suodatuksen jälkeen suodos, joka sisältää dimetyy- • i » *...· li-bis-(indenyyli) silaania, sekoitettiin uudelleen 42 g:n I 35 kanssa BOMAGR-A:ta ja ref luksoitiin 2 tuntia.After filtration, the filtrate containing dimethyl • bis (indenyl) silane was re-mixed with 42 g of BOMAGR-A and refluxed for 2 hours. hours.
t I t · • I 1 I · 116675 7t I t · • I 1 I · 116675 7
Sen jälkeen jäähdytettiin lämpötilaan -20 °C ja saostunut kiintoaine eristettiin ja kuivattiin olosuhteissa 100 °C/0,1 mbar.It was then cooled to -20 ° C and the precipitated solid was isolated and dried at 100 ° C / 0.1 mbar.
Voitiin eristää 15,1 g (97 % teoreettisesta) val-5 koista kiintoainetta.15.1 g (97% of theory) of white solids could be isolated.
Me2Si(indenyyli)2Mg:Me 2 Si (indenyl) 2 Mg
Mg: (laskettu: 7,8 %) saatu: 7,75 % 1H-NMR: (DMSO) 7,4 (d, 2H) ; 7,1 (d, 2H) ; 6,65 (d, 2H); 6,25 (t, 2H); 6,15 (t, 2H); 5,8 (d, 2H); 0,4 (s, 6H).Mg: (calculated: 7.8%) found: 7.75% 1H NMR: (DMSO) 7.4 (d, 2H); 7.1 (d, 2H); 6.65 (d, 2H); 6.25 (t, 2H); 6.15 (t, 2H); 5.8 (d, 2H); 0.4 (s, 6H).
10 Esimerkki 3 a) Me2Si[ (Me4Cp) (NfcBu) ]Mg:n valmistus 10 g (= 40 mmol) Me2Si [ (Me4CpH) (fcBuNH)] :ta (kirjallisuus: Organometallics, 9 (1990) 867) lisättiin huoneen lämpötilassa 48 ml:aan BOMAGR-A:ta (40 mmol) ja refluksoi-15 tiin 3 tuntia. Sen jälkeen liuos jäähdytettiin lämpötilaan -40 °C ja saostunut kiintoaine eristettiin (10,5 g; 99 % teoreettisesta).Example 3 a) Preparation of Me2Si [(Me4Cp) (NfcBu)] Mg 10 g (= 40 mmol) of Me2Si [(Me4CpH) (fcBuNH)] (Literature: Organometallics, 9 (1990) 867) was added at room temperature. 48 ml of BOMAGR-A (40 mmol) and refluxed for 3 hours. The solution was then cooled to -40 ° C and the precipitated solid was isolated (10.5 g; 99% of theory).
Mg: (laskettu: 8,9 %) saatu: 8,7 % 1H-NMR: (DMSO) 1,99 (s, 6H, Me2Cp) ; 1,79 (s, 6H, 20 Me2Cp) ; 1,09 (s, 9H, Me3C) ; 0,12 (s, 6H, Me2Si) b) Me2SI [ (Me4Cp) ^BuN) ] ZrCl2 : n valmistusMg: (calculated: 8.9%) found: 8.7% 1 H NMR: (DMSO) 1.99 (s, 6H, Me 2 Cl); 1.79 (s, 6H, 20 Me 2 Cl); 1.09 (s, 9H, Me 3 C); 0.12 (s, 6H, Me2Si) b) Preparation of Me2SI [(Me4Cp) ^ BuN)] ZrCl2
Lisättiin 12 g (48 mmol) Me2Si[(Me4Cp) (tBuNH)]:ta huoneenlämpötilassa 40 g:aan BOMAGR-A:ta (1,2 mol/kg; 48 mmol), joka oli 250 ml:n lasikolvissa, ja refluksoitiin 2 ; ’·. 25 tuntia.12 g (48 mmol) Me2Si [(Me4Cp) (tBuNH)] was added at room temperature to 40 g BOMAGR-A (1.2 mol / kg; 48 mmol) in a 250 mL glass flask and refluxed. 2; '·. 25 hours.
: : : Tämä juuri valmistettu liuos siirrettiin nopeasti suspensioon, joka sisälsi 11,2 g ZrCl4:a (48 mmol) 150This freshly prepared solution was rapidly transferred to a suspension of 11.2 g ZrCl4 (48 mmol) in 150
t « It «I
: ml:ssa dietyylieetteriä, lämpötilassa -20 °C.in ml of diethyl ether at -20 ° C.
> * I> * I
‘ Sen jälkeen annettiin lämmetä 1 tunnin aikana huo- i > « ’·* ' 30 neenlämpötilaan ja ref luksoitiin vielä 1 tunti.'It was then allowed to warm to room temperature over 1 hour and refluxed for an additional 1 hour.
Sen jälkeen muodostunut magnesiumsuola erotettiin ;,· | suodattamalla, kirkas suodos haihdutettiin tilavuuteen 40 ml ja jäähdytettiin lämpötilaan -20 °C.The resulting magnesium salt was then separated; by filtration, the clear filtrate was evaporated to a volume of 40 ml and cooled to -20 ° C.
Voitiin eristää 15,8 g Me2Si [ (Me4Cp) (tBuN) ] ZrCl2: ta 35 (38,4 mmol; 80 % teoreettisesta).15.8 g of Me2Si [(Me4Cp) (tBuN)] ZrCl2 35 (38.4 mmol; 80% of theory) could be isolated.
1H—NMR (CDCla) : 0,62 (s, 6H, Me2Si); 1,4 (s, 9H, * Me3C); 2,12 (s, 6H, Me2Cp) ; 2,2 ppm (s, 6H, Me2Cp) .1 H-NMR (CDCl 3): 0.62 (s, 6H, Me 2 Si); 1.4 (s, 9H, * Me 3 C); 2.12 (s, 6H, Me 2 Cl); 2.2 ppm (s, 6H, Me 2 Cl).
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Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4406110A DE4406110A1 (en) | 1994-02-25 | 1994-02-25 | Bridged cyclopentadienyl magnesium compounds and process for their preparation and their use in the production of metallocenes |
| DE4406110 | 1994-02-25 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| FI950871A0 FI950871A0 (en) | 1995-02-24 |
| FI950871A FI950871A (en) | 1995-08-26 |
| FI116675B true FI116675B (en) | 2006-01-31 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FI950871A FI116675B (en) | 1994-02-25 | 1995-02-24 | Cyclopentadienylmagnesium bridges, process for their preparation and their use in the preparation of metallocenes |
Country Status (12)
| Country | Link |
|---|---|
| US (2) | US5474716A (en) |
| EP (1) | EP0669337B1 (en) |
| JP (1) | JP3599810B2 (en) |
| AT (1) | ATE197457T1 (en) |
| AU (1) | AU684327B2 (en) |
| CA (1) | CA2130398C (en) |
| DE (2) | DE4406110A1 (en) |
| ES (1) | ES2152278T3 (en) |
| FI (1) | FI116675B (en) |
| GR (1) | GR3035363T3 (en) |
| NO (1) | NO306554B1 (en) |
| PT (1) | PT669337E (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4406109A1 (en) * | 1994-02-25 | 1995-08-31 | Witco Gmbh | Process for the production of bridged stereorigid metallocenes |
| US5563284A (en) * | 1994-09-09 | 1996-10-08 | Phillips Petroleum Company | Cyclopentadienyl-type ligands, metallocenes, catalyst systems, preparation, and use |
| DE4434640C1 (en) * | 1994-09-28 | 1996-02-01 | Hoechst Ag | Bridged metallocene prodn. in-situ |
| DE19523595A1 (en) * | 1995-06-30 | 1997-01-02 | Hoechst Ag | Process for the preparation of a carbon-bridged biscyclopentadiene compound |
| ES2166465T3 (en) * | 1995-09-07 | 2002-04-16 | Merck & Co Inc | PROCEDURE FOR THE PREPARATION OF DIMETHYLTITANOCENE. |
| DE19730880A1 (en) * | 1997-07-18 | 1999-01-21 | Basf Ag | Process for the selective production of racemic ansa-metallocene complexes |
| US6136995A (en) * | 1997-11-07 | 2000-10-24 | Sumitomo Chemical Company, Limited | Process for producing aminosilane compounds |
| US6095809A (en) | 1998-09-09 | 2000-08-01 | 3M Innovative Properties Company | Orthodontic archwire having reduced stiffness |
| WO2000024723A1 (en) | 1998-10-28 | 2000-05-04 | Merck & Co., Inc. | Stabilization of the reagent dimethyl titanocene |
| US6175027B1 (en) * | 1999-06-01 | 2001-01-16 | Boulder Scientific Company | Synthesis of bis (alkyl cyclopentadienyl) metallocenes |
| JP3864716B2 (en) * | 2001-03-13 | 2007-01-10 | 日産自動車株式会社 | Engine room harness wiring structure |
| JP5348202B2 (en) * | 2011-08-19 | 2013-11-20 | 宇部興産株式会社 | High purity bis (cyclopentadienyl) magnesium and process for producing the same |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE480390C (en) * | 1926-06-06 | 1929-08-02 | Fred Albert Oddie | Machine for bending rod-shaped metal pieces, such as pipes, profile rods, etc. like |
| US3306917A (en) * | 1965-08-02 | 1967-02-28 | Ethyl Corp | Process for preparing group viii metal cyclopentadienyl compounds |
| US4447369A (en) * | 1982-04-16 | 1984-05-08 | Ethyl Corporation | Organomagnesium compounds |
| US5055438A (en) * | 1989-09-13 | 1991-10-08 | Exxon Chemical Patents, Inc. | Olefin polymerization catalysts |
| IL89525A0 (en) * | 1988-03-21 | 1989-09-10 | Exxon Chemical Patents Inc | Silicon-bridged transition metal compounds |
| DE3927257A1 (en) * | 1989-08-18 | 1991-02-21 | Hoechst Ag | METHOD FOR PRODUCING A POLYOLEFIN |
| NZ235032A (en) * | 1989-08-31 | 1993-04-28 | Dow Chemical Co | Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component |
| DE4032266A1 (en) * | 1990-10-11 | 1992-04-16 | Hoechst Ag | METHOD FOR PRODUCING A POLYOLEFIN |
| US5721185A (en) * | 1991-06-24 | 1998-02-24 | The Dow Chemical Company | Homogeneous olefin polymerization catalyst by abstraction with lewis acids |
| NL9101502A (en) * | 1991-09-06 | 1993-04-01 | Dsm Nv | A METHOD FOR PREPARING A BRIDGED METALLOCENE COMPOUND, A CATALYST COMPONENT AND A METHOD FOR THE POLYMERIZATION OF OLEFINS. |
| US5231205A (en) * | 1991-09-23 | 1993-07-27 | Board Of Regents Of The University Of Nebraska | Preparation and use of (2-butene-1,4-diyl)magnesium complexes in organic synthesis |
| US5359105A (en) * | 1993-11-01 | 1994-10-25 | Albemarle Corporation | Deprotonation of cyclopentadienyl derivatives |
| DE4402192A1 (en) * | 1994-01-26 | 1995-07-27 | Witco Gmbh | Process for the preparation of biscyclopentadienyl compounds |
-
1994
- 1994-02-25 DE DE4406110A patent/DE4406110A1/en not_active Withdrawn
- 1994-08-05 AT AT94112300T patent/ATE197457T1/en not_active IP Right Cessation
- 1994-08-05 EP EP94112300A patent/EP0669337B1/en not_active Expired - Lifetime
- 1994-08-05 DE DE59409581T patent/DE59409581D1/en not_active Expired - Lifetime
- 1994-08-05 PT PT94112300T patent/PT669337E/en unknown
- 1994-08-05 ES ES94112300T patent/ES2152278T3/en not_active Expired - Lifetime
- 1994-08-18 CA CA002130398A patent/CA2130398C/en not_active Expired - Fee Related
- 1994-12-29 NO NO945079A patent/NO306554B1/en not_active IP Right Cessation
-
1995
- 1995-02-02 AU AU11529/95A patent/AU684327B2/en not_active Ceased
- 1995-02-22 US US08/392,390 patent/US5474716A/en not_active Expired - Lifetime
- 1995-02-22 US US08/392,387 patent/US5453221A/en not_active Expired - Lifetime
- 1995-02-23 JP JP3560395A patent/JP3599810B2/en not_active Expired - Fee Related
- 1995-02-24 FI FI950871A patent/FI116675B/en not_active IP Right Cessation
-
2001
- 2001-02-05 GR GR20010400188T patent/GR3035363T3/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| GR3035363T3 (en) | 2001-05-31 |
| PT669337E (en) | 2001-03-30 |
| JPH07252263A (en) | 1995-10-03 |
| FI950871A0 (en) | 1995-02-24 |
| US5474716A (en) | 1995-12-12 |
| CA2130398A1 (en) | 1995-08-26 |
| NO306554B1 (en) | 1999-11-22 |
| US5453221A (en) | 1995-09-26 |
| ATE197457T1 (en) | 2000-11-11 |
| FI950871A (en) | 1995-08-26 |
| DE59409581D1 (en) | 2000-12-14 |
| DE4406110A1 (en) | 1995-08-31 |
| EP0669337A2 (en) | 1995-08-30 |
| NO945079D0 (en) | 1994-12-29 |
| CA2130398C (en) | 1999-03-23 |
| AU1152995A (en) | 1995-09-07 |
| NO945079L (en) | 1995-08-28 |
| JP3599810B2 (en) | 2004-12-08 |
| EP0669337B1 (en) | 2000-11-08 |
| EP0669337A3 (en) | 1997-10-08 |
| AU684327B2 (en) | 1997-12-11 |
| ES2152278T3 (en) | 2001-02-01 |
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